CN110193381A - A kind of NHPI-GPTMS-CoOX/SiO2Heterogeneous catalyst and its application and recovery method - Google Patents

A kind of NHPI-GPTMS-CoOX/SiO2Heterogeneous catalyst and its application and recovery method Download PDF

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CN110193381A
CN110193381A CN201910553876.1A CN201910553876A CN110193381A CN 110193381 A CN110193381 A CN 110193381A CN 201910553876 A CN201910553876 A CN 201910553876A CN 110193381 A CN110193381 A CN 110193381A
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nhpi
sio
gptms
coo
heterogeneous catalyst
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石国军
徐进杨
徐思浩
梁雨欣
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Yangzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C07C45/34—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds
    • C07C45/36—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties in unsaturated compounds in compounds containing six-membered aromatic rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
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    • Y02P20/584—Recycling of catalysts

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Abstract

The present invention relates to a kind of NHPI-GPTMS-CoO in heterogeneous catalyst technical fieldX/SiO2Heterogeneous catalyst and its application and recovery method, the present invention use coprecipitation preparation containing Co first2+CoOX/SiO2, then using covalent bond Graft Method that NHPI is immobilized in CoOX/SiO2On, NHPI-GPTMS-CoO is madeX/SiO2Catalyst.NHPI-GPTMS-CoOX/SiO2Middle cobalt element good dispersion, with carrier S iO2Form Si-O-Co key.In catalyst preparation process and catalysis toluene oxidation reaction process, cobalt element content is held essentially constant, and does not observe leaching phenomenon.NHPI is grafted by C-O-N key and silane coupling agent KH-560 (GPTMS), and GPTMS is bonded by Si-O-Si key with carrier.In use, the grafting key of NHPI will not be broken, NHPI is not lost significantly the catalyst circulation.In the toluene alkylation reaction that hexafluoroisopropanol makees solvent, catalyst shows good catalytic activity, selectivity and stability.

Description

A kind of NHPI-GPTMS-CoOX/SiO2Heterogeneous catalyst and its application and recovery method
Technical field
It is the present invention relates to heterogeneous catalyst technical field, in particular to a kind of by NHPI and its initiator Co2+It is immobilized altogether NHPI-GPTMS-CoOX/SiO2Heterogeneous catalyst and its in answering into the oxygen selectivity oxidized producing benzaldehyde of toluene liquid-phase molecule With and recovery method.
Background technique
Benzaldehyde is the important intermediate of fragrance, dyestuff, medicine and other fields.The source of industrial benzaldehyde mainly has two Kind: preparation is hydrolyzed as the byproduct of preparing phenylformic acid through liquid phase oxidation of methylbenzene and by benzyl chloride.The former main problem is oxidation Degree is difficult to control, and benzaldehyde is selectively low；Latter process is cumbersome, uses poisonous and hazardous reagent C l2, product containing chlorine element not It can be used for food, medicine field.
In recent years, with the increase of no chlorobenzaldehyde demand, the benzaldehyde preparation process of research and development efficiently, economic, environmentally friendly Cause researcher widely to think deeply.Other than toluene oxidation method, benzyl alcohol oxidation method, benzoic acid reduction method and styrene oxygen Change method is also being probed into always.However as raw material, toluene is more economical, has more the market competitiveness.The preparation of toluene oxidation method The main problem that benzaldehyde is faced is the excessive oxidation for how inhibiting or reducing benzaldehyde.Toluene, which is saturated C-H key, has power Inertia is learned, traditional activation method usually carries out under the harsh conditions of high temperature and pressure.Under these conditions, benzaldehyde was easy Degree oxidation, selectivity are lower.
NHPI is a kind of organic catalyst of high activity, can activate various hydro carbons under mild conditions.NHPI preparation Simply, it without toxicity, is easy to generate phthalimide NO free radical (PINO) under the action of initiator. PINO seizes Hydrogen Energy power with stronger, hydrogen atom can be seized from hydrocarbon compound, to activate substrate.Ishii etc. NHPI is used as toluene oxidation at first by (2001,343:393-427 Advanced Synthesis & Catalysis) The catalyst of reaction.Theirs studies have shown that acetic acid makees solvent, 10 mol% NHPI make catalyst, 0.5 mol% Co (OAc)2Make NHPI initiator, O2Make under the reaction condition of oxidant, 298 K of toluene reacts 20 h, and conversion ratio is more than 80%, but main Product is benzoic acid.(Angewandte Chemie, the International Edition 2017,56:5912 such as Pappo - 5915) discovery hexafluoroisopropanol has the function of inhibiting oxidation of Benzaldehyde.Under room temperature aerobic conditions, it is added in benzaldehyde The hexafluoroisopropanol of 1.5 equivalents does not observe that benzoic acid generates in 4 h.They also confirm hexafluoroisopropanol and benzene by nuclear-magnetism Intermolecular hydrogen bonding is formd between formaldehyde, further proves that the formation of hydrogen bond has delayed benzaldehyde to be oxidized by theoretical calculation Speed.They make solvent with hexafluoroisopropanol substitution acetic acid, under mild reaction conditions with reference to the catalyst system of Ishii Realize toluene high activity, with high selectivity to benzaldehyde conversion, benzaldehyde yield is more than 90%.
The NHPI/Co (OAc) of the research and development such as Pappo2/ HFIP reaction system is although be that toluene molecule oxygen selects by height praise Property oxidation producing benzaldehyde simple and perfect technique, but the system uses homogeneous catalyst, and separation is difficult, cost It is high.Furthermore it is reported that (Catalysis Letters. 2016,14:383-390), NHPI make catalyst there is also The problem of slowly decomposing and release micro by-product, polluted product increases the difficulty of purification.Can have NHPI is immobilized Solve these problems to effect.The supported method of NHPI mainly has infusion process and Graft Method.Infusion process is easy to operate, preparation it is more The activity of phase catalyst is suitable with homogeneous NHPI, but NHPI is easy to be lost in the reaction, and stability is poor.Graft Method passes through altogether NHPI and carrier are tied by valence link, and stability is good, and NHPI is not easily runed off.At present about in the supported research of NHPI, perhaps It is more still to use homogeneous initiator.These have researched and solved the separation and recovery problem of NHPI, and but having ignored initiator, there is phases As problem.
Summary of the invention
The present invention is in the oxygen selectivity oxidized heterogeneous catalyst recycling for preparing benzaldehyde of toluene molecule in the prior art There are the problem of provide it is a kind of by NHPI and its initiator Co2+It is common immobilized, prepare the NHPI-GPTMS-CoO easily recycledX/ SiO2Heterogeneous catalyst, which can realize repeatedly recycles repeatedly, and recovery method is simple, recycling rate of waterused It is high.
Present invention firstly provides a kind of NHPI-GPTMS-CoOX/SiO2Heterogeneous catalyst, be made by the steps:
1) coprecipitation preparation contains Co2+CoOX/SiO2: CoO is made by sodium metasilicate and cobalt nitrate co-precipitationX/ SiO2；
2) it is grafting transition substance using γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, passes through covalent bond Graft Method N-Hydroxyphthalimide is immobilized in CoOX/SiO2On, supported heterogeneous catalyst NHPI-GPTMS- altogether is made CoOX/SiO2, wherein the grafting density of NHPI is 0.3-1.0 mmol/g, and the content of Co is 2-6 mmol/g.
The present invention first uses coprecipitation preparation containing Co2+CoOX/SiO2, then NHPI is consolidated using covalent bond Graft Method It is loaded in CoOX/SiO2On, NHPI-GPTMS-CoO is madeX/SiO2Catalyst.NHPI-GPTMS-CoOX/SiO2Middle cobalt element dispersion Property is good, with carrier S iO2Form Si-O-Co key.In catalyst preparation process and catalysis toluene oxidation reaction process, cobalt member Cellulose content is held essentially constant, and NHPI is grafted by C-O-N key and silane coupling agent KH-560 (GPTMS), and GPTMS passes through Si-O-Si key is bonded with carrier.Compared with prior art, catalyst n HPI-GPTMS-CoO of the inventionX/SiO2It will NHPI and its initiator are jointly immobilized, have good stability, and can be recycled, and reduce the cost of catalyst.It is urged in the present invention The usage of agent meets the requirement of Green Chemistry, lower to equipment requirement.
Further, step 1) specifically includes following substep:
1.1) by suitable Co (NO3)2·6H2O is dissolved in deionized water, and compound concentration is the Co of 0.30-0.35 mmol/mL (NO3)2Solution moves into spare in constant pressure funnel A until completely dissolved；
1.2) by Na2SiO3·9H2O is dissolved in deionized water, and compound concentration is the Na of 0.20-0.65 mmol/mL2SiO3It is molten Liquid is fitted into constant pressure funnel B after being completely dissolved；
1.3) deionized water is injected in reactor C, it is under 363 K constant temperature, the solution in constant pressure funnel A and constant pressure funnel B is same When average rate be added dropwise in reactor C, the Co (NO3)2Solution, Na2SiO3Solution and deionized water are 3:3:4-6 by volume, After completion of dropwise addition, in 363 K the reaction was continued 0.5-1 h, it is transferred in 363 K baking ovens later and stands 12-for 24 hours, be obtained by filtration solid Precursor reactant object；
1.4) the resulting solid reactant of 1.3 steps is washed repeatedly with deionized water, then 5-15 times of solid volume of n-butanol In, it is evaporated liquid phase after mixing, obtained solid dries 12-for 24 hours in 393 K, roasts 3-in 673 K in still air After 6h, it is ground into powder, CoO is madeX/SiO2。
Further, step 2 includes following substep:
2.1) NHPI analog N, N'- dihydroxy pyromellitic acid imines, that is, NDHPI is prepared；The principle such as formula 1 of this step reaction:
2.2) NDHPI is reacted with GPTMS and prepares intermediate NHPI-GPTMS, wherein GPTMS is silane coupling agent KH-560； The principle such as formula 2 of this step reaction:
2.3) intermediate NHPI-GPTMS and CoOX/SiO2Reaction prepares heterogeneous catalyst NHPI-GPTMS-CoOX/SiO2, wherein The content of NHPI be 0.3-1.0 mmol/g, the principle of the reaction of this step such as formula 3:
。
Further, the 2.1) detailed process of step are as follows: the hydroxylamine hydrochloride of equimolar amounts and triethylamine are dissolved in anhydrous second In alcohol, wherein the proportional quantity of hydroxylamine hydrochloride and triethylamine and dehydrated alcohol is 30-35 mmol/100mL, and dehydrated alcohol is added The PDMA of volume 1/6, wherein PDMA is pyromellitic dianhydride, and 353 K back flow reaction, 8-12 h, reaction solution pours into 1.5 times of solution It in volumes of deionized water, filters after mixing evenly, N, the equal benzene of N'- dihydroxy is made in the dry 24-30h of 323 K in obtained solid Four acid imides, as NDHPI.
2.2) detailed process of step are as follows: by molar ratio is 1:3 2.1) NDHPI and silane coupling agent KH- made from step 560 are dissolved in ethyl acetate solution, and wherein NDHPI is 30-35 mmol/100mL with respect to the concentration of ethyl acetate solution, N224 h of back flow reaction under atmosphere, after reaction, by the isolated solid of Rotary Evaporators, with ethyl alcohol and methylene chloride Mixed liquor washing, it is dry, intermediate NHPI-GPTMS is made.
In above-mentioned 2.2 step, the volumetric usage of ethyl alcohol and methylene chloride ratio is 1:(1- in the mixed liquor of ethyl alcohol and methylene chloride 3).
The detailed process of 2.3 steps are as follows: by 7.5 mmol, 2.1 step) made from CoOX/SiO2With 0.5-1.5 mmol's 2.2) NHPI-GPTMS that step is prepared is thrown in toluene, and wherein NHPI-GPTMS is difference 1.5- with respect to methyl consumption proportion 5mmol/100mL, in N224-30 h of back flow reaction under the conditions of atmosphere protection, after reaction, filtering, is 1:1- with volume ratio The mixed solvent washing of 3 ether and chloroform, it is dry, NHPI-GPTMS-CoO is madeX/SiO2Heterogeneous catalyst.
To further realize the purpose of the present invention, the present invention also provides a kind of above-mentioned heterogeneous catalysts for toluene liquid-phase point The method that sub- selective oxidation prepares benzaldehyde, specifically, by above-mentioned NHPI-GPTMS-CoOX/SiO2Catalyst is placed in polytetrafluoro In the autoclave of ethylene liner, the toluene and hexafluoroisopropanol that molar ratio is 1:10-20 is added, wherein catalyst is with respect to first The amount of coming into operation of benzene is 0.1-0.2g/mmol, under conditions of 363 K, 2.0 MPa oxygen pressures, with 240 r/min magnetic agitations It after 5-8 h of lower reaction, is cooled to room temperature, is centrifugated solid phase and liquid phase, the liquid phase is that benzaldehyde obtained by selective oxidation produces Object, the solid phase are NHPI-GPTMS-CoOX/SiO2The recovery mixture of heterogeneous catalyst.Heterogeneous catalyst of the invention is used for Toluene alkylation is prepared in the method for benzaldehyde, easy to operate, and catalyst consumption is few, and recycling is convenient, may be implemented anti- Multiple circulation and stress uses.
Third mesh of the present invention is to provide a kind of liquid phase NHPI- for preparing above-mentioned selective oxidation and separating after benzaldehyde GPTMS-CoOX/SiO2The recovery mixture of heterogeneous catalyst recycles separating-purifying further in order to recycle point of Reusability From method of purification, specifically: by NHPI-GPTMS-CoOX/SiO2The recovery mixture ether and chloroform of heterogeneous catalyst Mixed solvent sufficiently wash to after washing 1 to 2 time again after colourless, in dry 24 h of 323 K, both recycle to obtain heterogeneous catalyst NHPI-GPTMS-CoOX/SiO2-Ry, the heterogeneous catalyst NHPI-GPTMS-CoOX/SiO2-RyIt can be repeatedly used for selective oxygen Change prepares benzaldehyde and catalyst recycling in use, wherein, subscript y represents the number that catalyst circulation uses.Of the invention is more Phase catalyst recycling, the homogeneous catalyst cumbersome compared to separating step, the heterogeneous catalyst pass through centrifuge separation, operation letter It is single.During the recycling of catalyst, supported NHPI and its initiator Co2+It has good stability, does not flow significantly It loses.
Further, the volume ratio of the in the mixed solvent ether of the ether and chloroform and chloroform is 1:1-3.
Detailed description of the invention
Fig. 1 is NHPI-GPTMS-CoO of the inventionX/SiO2The preparation flow figure of heterogeneous catalyst.
Fig. 2 is CoOX/SiO2Infrared spectroscopy (A), high-resolution-ration transmission electric-lens figure (B) and cobalt element distribution map (C).
Fig. 3 be presoma NDHPI and pyromellitic dianhydride PMDA) infrared spectrogram.
The infrared spectroscopy of Fig. 4 GPTMS, NHPI-GPTMS and NDHPI.
Fig. 5 CoOX/SiO2、NHPI-GPTMS-CoOX/SiO2With the infrared spectroscopy of NHPI-GPTMS.
Fig. 6 (A) and 6(B) be CoOX/SiO2, fresh catalyst NHPI-GPTMS-CoOX/SiO2With recycling catalyst NHPI-GPTMS-CoOX/SiO2-R1、NHPI-GPTMS-CoOX/SiO2-R5Thermogravimetric curve and differential thermogravimetric curve.
Specific embodiment
Below by specific comparative example and embodiment, the present invention is further analyzed, explanation, comparison.
Comparative example 1
This comparative example is added without any catalyst for toluene alkylation blank assay.
In the autoclave of the polytetrafluoroethyllining lining of 50 mL, the toluene of 2 mmol, the solvent of 40 mmol is added Hexafluoroisopropanol is 363 K in reaction temperature, and magnetic agitation rotating speed is 240 r/min and oxygen pressure is the condition of 2.0 MPa 5 h of lower reaction, are cooled to room temperature, sampling analysis reactant composition is as shown in table 1 after reaction.
Embodiment 1
Heterogeneous catalyst NHPI-GPTMS-CoO is prepared by process as shown in Figure 1 firstX/SiO2, preparation step are as follows:
A) 2.91 g Co (NO are weighed3)2·6H2O and 2.84 g Na2SiO3·9H2O is dissolved in respectively in 30 mL deionized waters, and Stream is added dropwise to 40 mL deionized waters, and 363 K are stirred to react 0.5 h.It is placed in 363 K baking ovens and stands 24 h.Filtering, filter cake are used Deionized water is washed repeatedly；40 mL n-butanols are added, after being sufficiently mixed with solid, 353 K are evaporated n-butanol；Obtained solid is first In dry 12 h of 393 K, 3 h are then roasted in 673 K still airs, obtain CoO after grindingX/SiO2.As shown in Fig. 2 A CoOX/SiO2Infrared spectroscopy (A), high-resolution-ration transmission electric-lens figure (B) and cobalt element distribution map (C), CoOX/SiO2It is red External spectrum shows that cobalt and silica supports form Si-O-Co key (1016 cm-1), high-resolution-ration transmission electric-lens shown in Fig. 2 B Figure shows CoOX/SiO2Surface does not have apparent crystal morphology feature, and cobalt element distribution map shows CoO as shown in fig. 2 cX/ SiO2Middle cobalt element dispersibility is preferably.
B) 2.78 g hydroxylamine hydrochlorides are weighed, 5.2 mL triethylamines of measurement are dissolved in 120 mL dehydrated alcohols, addition 4.36 G pyromellitic dianhydride, 353 K back flow reaction, 8 h, reaction solution pour into 200 mL deionized waters, stir, and filtering, solid is in 323 K dries 24 h, and NDHPI is made.As shown in figure 3, being presoma NDHPI and pyromellitic dianhydride (PMDA) for the present embodiment Infrared spectroscopy.By comparing it can be found that in PMDA spectrogram, 1231 cm-1Locate the characteristic absorption peak of cyclic acid anhydride C-O-C There was only the intensity of very little in NDHPI spectrogram, shows that cyclic acid anhydride is reacted；NDHPI spectrogram is in 3448 cm-1With 3529 cm-1 There are two sharp new absorption peaks in place, belongs to the symmetrical and asymmetric stretching vibration peak of N-OH.This all shows PMDA Reaction generates NDHPI.
C) 1 g step the b NDHPI being prepared and 2.8 mL silane coupling agent KH-560 (GPTMS) are dissolved in 120 In mL ethyl acetate solution, in N224 h of back flow reaction under atmosphere, after reaction, revolving obtain solid, are 1:1 with volume ratio Ethyl alcohol and the washing of methylene chloride mixed liquor, it is dry, NHPI-GPTTMS is made.As shown in figure 4, NDHPI, silane coupling agent KH- The infrared spectroscopy of 560 (GPTMS) and the NHPI-GPTMS of the two reaction preparation, by comparing it can be found that NHPI-GPTMS Other than the characteristic peak all comprising NDHPI, also in 904 cm-1There is the feature peak-to-peak signal of GPTMS in place, belongs to C-H Out-of-plane bending vibration absorption peak.This shows that NHPI-GPTMS is successfully prepared.
D) CoO for obtaining 1 g step aX/SiO2The NHPI-GPTTMS that carrier and step c are prepared is placed in 30mL first In benzole soln, in N2373 K back flow reaction, 24 h under atmosphere, after reaction, filtering, the ether and three for being 1:1 with volume ratio The mixed solvent of chloromethanes washs, dry, and heterogeneous catalyst NHPI-GPTMS-CoO is madeX/SiO2.As shown in figure 5, catalyst NHPI-GPTMS-CoOX/SiO2In addition to showing support C oOX/SiO2All characteristic peaks other than, also in 1692 cm-1With 1780 cm-1There is symmetrical, the asymmetric stretching vibration peak of carbonyl in place, in 3448 cm-1With 3529 cm-1There is the symmetrical of N-OH in place And asymmetric stretching vibration peak.This shows that NHPI is successfully grafted on CoOX/SiO2On.
By heterogeneous catalyst NHPI-GPTMS-CoO made from above-mentioned steps dX/SiO20.2 g is placed in the polytetrafluoro of 50 mL In the autoclave of ethylene liner, the raw material toluene of 2 mmol, the solvent hexafluoroisopropanol of 40 mmol is added, in reaction temperature Degree be 363 K, magnetic agitation rotating speed be 240 r/min and oxygen pressure be 2.0 MPa under conditions of react 5 h, reaction terminates After be cooled to room temperature, be centrifugated solid phase and liquid phase, wherein liquid phase is benzaldehyde product obtained by selective oxidation, and solid phase is NHPI-GPTMS-CoOX/SiO2The recovery mixture of heterogeneous catalyst.Benzene is carried out to liquid-phase reaction product made from the present embodiment Formaldehyde activity analysis such as table 1.
Embodiment 2
This implementation will prepare the solid phase NHPI-GPTMS-CoO obtained after benzaldehyde first in embodiment 1X/SiO2Heterogeneous catalyst Recovery mixture carry out separation and recovery purification as follows: with volume ratio be 1:1 ether and chloroform mixing it is molten Agent washing, dry 24 h of 323 K obtain one cycle recycling catalyst n HPI-GPTMS-CoOX/SiO2-R1。
Catalyst n HPI-GPTMS-CoO is recycled with the one cycle againX/SiO2-R1Benzene first is prepared as described in Example 1 Aldehyde weighs 0.2 g NHPI-GPTMS-CoOX/SiO2-R1It is placed in the autoclave of the polytetrafluoroethyllining lining of 50 mL, adds Enter the raw material toluene of 2 mmol, the solvent hexafluoroisopropanol of 40 mmol, is 363 K in reaction temperature, magnetic agitation rotating speed is 240 r/min and oxygen pressure react 5 h under conditions of being 2.0 MPa, are cooled to room temperature after reaction, are centrifugated solid phase And liquid phase, wherein liquid phase is benzaldehyde product obtained by selective oxidation, solid phase NHPI-GPTMS-CoOX/SiO2-R1Multiphase is urged The recovery mixture of agent.Benzaldehyde activity analysis such as table 1 is carried out to liquid-phase reaction product made from the present embodiment.
Embodiment 3
In the present embodiment, gained solid phase is NHPI-GPTMS-CoO after embodiment 2 is prepared benzaldehydeX/SiO2-R1Multiphase urge The recovery mixture of agent obtains the catalyst n HPI-GPTMS- of secondary recovery by the separation and recovery method of purification of embodiment 2 CoOX/SiO2-R2。
Use NHPI-GPTMS-CoO as described in Example 2 againX/SiO2-R2It is anti-to liquid phase for catalyst preparation benzaldehyde Product is answered to carry out benzaldehyde activity analysis such as table 1.Separation and recovery purification of the solid phase recovery mixture for subsequent cycle recycles again With.
Embodiment 4
First as described in Example 2, solid phase recovery mixture obtained in embodiment 3 is obtained into separation and recovery purification is carried out The catalyst n HPI-GPTMS-CoO recycled three timesX/SiO2-R3, then as described in Example 2 with the catalyst recycled three times, Benzaldehyde is prepared, benzaldehyde activity analysis such as table 1 is carried out to liquid-phase reaction product.Solid phase recovery mixture is for subsequent cycle Separation and recovery purification Recycling.
Embodiment 5
First as described in Example 2, solid phase recovery mixture obtained in embodiment 4 is obtained into separation and recovery purification is carried out The catalyst n HPI-GPTMS-CoO of four recyclingX/SiO2-R4, then the catalyst recycled with this four times is as described in Example 2, Benzaldehyde is prepared, benzaldehyde activity analysis such as table 1 is carried out to liquid-phase reaction product.Solid phase recovery mixture presses 2 side of embodiment again Method carries out recycling separating-purifying, obtains the 5th catalyst n HPI-GPTMS-CoO addedX/SiO2-R5。
。
As shown in fig. 6, for fresh CoO made from embodiment 1X/SiO2, fresh catalyst NHPI-GPTMS-CoOX/SiO2、 The recycling catalyst n HPI-GPTMS-CoO of embodiment 2X/SiO2-R1With the recycling catalyst n HPI-GPTMS- of embodiment 5 CoOX/SiO2-R5Thermogravimetric curve and differential thermogravimetric curve.CoOX/SiO2Mass loss mainly before 393 K, due to Adsorb the desorption of water.The thermogravimetric curve of catalyst and recycling catalyst is almost the same, and the pervious mass loss of 513 K is attributed to suction The desorption of attached water and constitution water, the mass loss of 513 K or more are the dehydration contractings of the decomposition and silicone hydroxyl due to grafting organic matter It closes.This shows that catalyst is recycled 5 times in the toluene oxidation reaction that fluorinated alohol makees solvent, and the NHPI of grafting still deposit by stabilization ?.

Claims (10)

1. a kind of NHPI-GPTMS-CoOX/SiO2Heterogeneous catalyst, it is characterized in that: being made by the steps:
Coprecipitation preparation contains Co2+CoOX/SiO2: CoO is made by sodium metasilicate and cobalt nitrate co-precipitationX/SiO2,；
2) it is grafting transition substance using γ-(2,3- the third oxygen of epoxy) propyl trimethoxy silicane, passes through covalent bond Graft Method N-Hydroxyphthalimide is immobilized in CoOX/SiO2On, supported heterogeneous catalyst NHPI-GPTMS- altogether is made CoOX/SiO2, wherein the grafting density of NHPI is 0.3-1.0 mmol/g, and the content of Co is 2-6 mmol/g.
2. heterogeneous catalyst according to claim 1, which is characterized in that step 1) specifically includes following substep:
1.1) by suitable Co (NO3)2·6H2O is dissolved in deionized water, and compound concentration is the Co of 0.30-0.35 mmol/mL (NO3)2Solution moves into spare in constant pressure funnel A until completely dissolved；
1.2) by Na2SiO3·9H2O is dissolved in deionized water, and compound concentration is the Na of 0.20-0.65 mmol/mL2SiO3Solution, It is fitted into after being completely dissolved in constant pressure funnel B；
1.3) deionized water is injected in reactor C, it is under 363 K constant temperature, the solution in constant pressure funnel A and constant pressure funnel B is same When average rate be added dropwise in reactor C, the Co (NO3)2Solution, Na2SiO3Solution and deionized water are 3:3:4-6 by volume, After completion of dropwise addition, in 363 K the reaction was continued 0.5-1 h, it is transferred in 363 K baking ovens later and stands 12-for 24 hours, be obtained by filtration solid Precursor reactant object；
1.4) the resulting solid reactant of 1.3 steps is washed repeatedly with deionized water, is being then dissolved in 5-15 times of solid volume just In butanol, it is evaporated liquid phase after mixing, obtained solid dries 12-for 24 hours in 393 K, roasts in still air in 673 K After burning 3-6h, it is ground into powder, CoO is madeX/SiO2。
3. heterogeneous catalyst according to claim 2, which is characterized in that step 2 includes following substep:
2.1) NHPI analog N, N'- dihydroxy pyromellitic acid imines, that is, NDHPI is prepared；
2.2) NDHPI is reacted with GPTMS and prepares intermediate NHPI-GPTMS, wherein GPTMS is silane coupling agent KH-560；
2.3) reaction equation 3, intermediate NHPI-GPTMS and CoO are pressedX/SiO2Reaction prepares heterogeneous catalyst NHPI-GPTMS- CoOX/SiO2, wherein the content of NHPI is 0.3-1.0 mmol/g.
4. heterogeneous catalyst according to claim 3, which is characterized in that 2.1) in step: by the hydroxylamine hydrochloride of equimolar amounts It is dissolved in dehydrated alcohol with triethylamine, wherein the proportional quantity of hydroxylamine hydrochloride and triethylamine and dehydrated alcohol is 30-35 The PDMA of dehydrated alcohol volume 1/6 is added in mmol/100mL, and wherein PDMA is pyromellitic dianhydride, 353 K back flow reactions 8- 12 h, reaction solution are poured into 1.5 times of liquor capacity deionized waters, are filtered after mixing evenly, and obtained solid is in 323 K dry 24- N, N'- dihydroxy pyromellitic acid imines, as NDHPI is made in 30h.
5. heterogeneous catalyst according to claim 3, which is characterized in that 2.2) in step: being the 2.1 of 1:3 by molar ratio) step NDHPI and silane coupling agent KH-560 obtained is dissolved in ethyl acetate solution, and wherein NDHPI is with respect to ethyl acetate solution Concentration be 30-35 mmol/100mL, in N224 h of back flow reaction is separated by Rotary Evaporators after reaction under atmosphere Solid is obtained, is washed with the mixed liquor of ethyl alcohol and methylene chloride, it is dry, intermediate NHPI-GPTMS is made.
6. heterogeneous catalyst according to claim 5, which is characterized in that in the mixed liquor of ethyl alcohol and methylene chloride ethyl alcohol and The volumetric usage ratio of methylene chloride is 1:1-3.
7. heterogeneous catalyst according to claim 3, which is characterized in that in 2.3 steps: by 7.5 mmol, 2.1 step) it is made CoOX/SiO2With the 2.2 of 0.5-1.5 mmol) NHPI-GPTMS that is prepared of step throws in toluene, wherein NHPI- GPTMS is difference 1.5-5mmol/100mL with respect to methyl consumption proportion, in N2Back flow reaction 24-30 under the conditions of atmosphere protection H, after reaction, filtering, the mixed solvent of the ether and chloroform that are 1:1-3 with volume ratio are washed, dry, are made NHPI-GPTMS-CoOX/SiO2Heterogeneous catalyst.
8. a kind of method that benzaldehyde is prepared using heterogeneous catalyst selective oxidation described in any one of claim 1-7, It is characterized in that, by NHPI-GPTMS-CoOX/SiO2Catalyst is placed in the autoclave of polytetrafluoroethyllining lining, and addition rubs You are than the toluene and hexafluoroisopropanol that are 1:10-20, and wherein catalyst is 0.1-0.2 g/ relative to the ratio that comes into operation of toluene Mmol after reacting 5-8 h under 240 r/min magnetic agitations, is cooled under conditions of 363 K, 2.0 MPa oxygen pressures Room temperature is centrifugated solid phase and liquid phase, and the liquid phase is benzaldehyde product obtained by selective oxidation, and the solid phase is NHPI- GPTMS-CoOX/SiO2The recovery mixture of heterogeneous catalyst.
9. a kind of recovery method of the heterogeneous catalyst in method of benzaldehyde according to any one of claims 8, which is characterized in that will NHPI-GPTMS-CoOX/SiO2The mixed solvent of the recovery mixture of heterogeneous catalyst ether and chloroform sufficiently wash to After washing 1 to 2 time again after colourless, in dry 24 h of 323 K, both recycle to obtain heterogeneous catalyst NHPI-GPTMS-CoOX/SiO2- Ry, the heterogeneous catalyst NHPI-GPTMS-CoOX/SiO2-RyIt can be repeatedly used for selective oxidation and prepare benzaldehyde and catalyst Recycling is in use, wherein, subscript y represents the number that catalyst circulation uses.
10. recovery method according to claim 9, which is characterized in that the in the mixed solvent of the ether and chloroform The volume ratio of ether and chloroform is 1:1-3.
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